Solid alkylbenzene sulfonates and cleaning compositions having enhanced water hardness tolerance

ABSTRACT

This invention is directed to detergent compositions which employ sulfonated linear alkylbenzenes as surfactants, wherein the sulfonated linear alkylbenzenes have a higher content of the sulfonated 2-phenyl alkylbenzene isomers than was previously available in sulfonated phenyl alkylbenzene surfactants of the prior art. Cleaning compositions according to the invention are more effective as cleaning agents over their counterparts of prior art which contain sulfonated linear alkylbenzenes having lower contents of the 2-phenyl alkylbenzene isomers, owing to an unexpected increase in tolerance of water hardness minerals normally associated with precipitation of the active detergent agent. Solid sulfonate salts of alkylbenzenes are also provided, including dry formulations containing same.

This application is a continuation-in-part application of applicationSer. No. 08/598,692, filed Feb. 8, 1996, now U.S. Pat. No. 5,847,254 andof application Ser. No. 08/879,745, filed Jun. 20, 1997, now U.S. Pat.No. 6,315,964 which is a divisional of Ser. No. 08/598,695, filed Feb.8, 1996, now U.S. Pat. No. 5,770,782, the contents of which areexpressly incorporated herein by reference. This Application claims thebenefit of U.S. Provisional Application No. 60/178,823 filed Jan. 28,2000, which is currently still pending.

BACKGROUND OF THE INVENTION

This invention relates generally to detergent compositions and cleaningcompositions having enhanced detergency and cleaning capabilities. Itrelates more particularly to detergent and cleaning compositionscontaining the 2-phenyl isomer of linear alkylbenzene sulfonates inconcentrations higher than were previously available in the prior art,owing to the discovery of the revolutionary catalyst and process forproducing such isomers in high concentration, as detailed herein.

Chemical compounds useful for removing grease, oils, dirt and otherforeign matter from various surfaces and objects have been known forsome time, including the simple soaps which are manufactured by thesaponification of oils (including animal fats and vegetable oils).Saponification is essentially a process whereby aqueous alkali metalhydroxide is mixed with an ester (such as an animal fat or vegetableoil) to cause de-esterification of the ester with the formation of thealkali salt(s) of the carboxylic acid(s) from which the ester wasderived, which salt(s) are typically very soluble in aqueous media.Importantly, the anion portions of such alkali salts of the carboxylicacid(s) include as part of their molecular structure a hydrophilicportion, i.e., the carboxylate function, which is highly attracted towater molecules. Such salts also include a hydrophobic portion as partof their molecular structure, which is typically a hydrocarbon-basedportion containing between about 12 and 22 carbon atoms per molecule.Such salts are commonly referred to by those skilled in the art as“salts of fatty acids”, and are often commonly referred to by laypersonsas “soap”. Aqueous solutions of salts of fatty acids are very effectiveat causing grease, oils, and other normally water-insoluble materials tobecome soluble and thus capable of being rinsed away, thus leavingbehind a clean substrate which may typically comprise a tabletop,countertop, article of glassware or dinnerware, flatware, clothing,architecture, motor vehicle, human skin, human hair, etc.

While the industries for the production of such soaps from fats and oilsare now well-established, saponification chemists and other workers havecontinuously sought improved chemistry for rendering materials which arenot normally soluble in aqueous media to become soluble therein. Towardsthis end, a wide variety of materials have been identified by thoseskilled in the art, with the common denominator of such materials beingthat the materials all contain a hydrophobic portion and a hydrophilicportion in their molecular structures.

One family of materials that have been identified as suitable soapsubstitutes are the linear alkylbenzene sulfonates (“LAB sulfonates”).The LAB sulfonates in general are exemplified as comprising a benzenering structure having a hydrocarbyl substituent (or “alkyl substituent”)and a sulfonate group bonded to the ring in the para position withrespect to one another. The length of the hydrocarbon chain of the alkylsubstituent on the ring is selected to provide a high level ofdetergency characteristics while the linearity of the hydrocarbon chainenhances the biodegradability characteristics of the LAB sulfonate. Thehydrocarbyl substituent may typically contain 6, 7, 8, 9, 10, 11, 12,13, 14 or 15 carbon atoms (the “detergent range”) in a substantiallylinear arrangement, and may be attached to the benzene ring through aconventional Friedel-Crafts alkylation process using a correspondingolefin and employing a Lewis acid catalyst such as aluminum chloride andconditions known to those skilled in the art as useful for suchalkylations. Various alkylation processes useful for production ofalkylbenzenes are described in U.S. Pat. Nos. 3,342,888; 3,478,118;3,631,123; 4,072,730; 4,301,316; 4,301,317; 4,467,128; 4,503,277;4,783,567; 4,891,466; 4,962,256; 5,012,021; 5,196,574; 5,302,732;5,344,997; and 5,574,198, as well as European patent application 353813and Russian patent 739,046, the entire contents of which areincorporated herein by reference thereto.

Once a hydrocarbyl radical has been appended to a benzene ring inaccordance with the foregoing, the resulting linear alkylbenzene mustsubsequently be sulfonated in order to produce a finished detergentmaterial that is capable of solubilizing grease, oils, dirt, and thelike from various substrates, such as dishes, motorized vehicles, hardsurfaces, architecture, and fabrics, to name but a few. Sulfonation is aknown chemical process whose reactants and conditions are known to thoseskilled in the chemical arts. Through the process of sulfonation, asulfonate group is caused to become chemically bonded to a carbon atomin the benzene ring structure of the linear alkylbenzene, thus providingthe molecule as a whole with a hydrophilic sulfonate group in additionto the hydrophobic hydrocarbyl portion.

It is known that during the course of mono-alkylation of the benzenering to introduce a hydrocarbon tail into the molecular structure,several structural isomers are possible in which the benzene ring isattached to various points along the hydrocarbon chain used. It isgenerally believed that steric effects of the mono-olefin employed playa role in the distribution of isomers in the mono-alkylated product, inaddition to the catalyst characteristics and reaction conditions. Thus,it is possible for a single benzene ring to become attached to, say, the2, 3, 4, or 5 positions in a 10 carbon atom linear mono-olefin, with adifferent alkylbenzene isomer being produced in each such case.Sulfonation of such different materials results in as many differentalkylbenzene sulfonates, each of which have different solubilizationcapabilities with respect to various oils, grease, and dirt, etc.

The sulfonates of the 2-phenyl alkyl isomers are regarded by thoseskilled in the art as being very highly desirable materials, assulfonated linear alkylbenzene detergent materials made from sulfonationof the 2-phenyl alkyl materials have superior cleaning and detergencypowers with respect to the sulfonation products of other isomersproduced during the alkylation. The general structure of the mostdesired 2-phenyl alkyl isomer products may be defined as:

which in a preferred embodiment has n equal to any integer selected fromthe group consisting of: 5, 6, 7, 8, 9, 10, 11, and 12. Since theFriedel-Crafts type alkylation employed to produce 2-phenyl alkylisomers according to the invention may often utilize a mixture ofolefins in the detergent range (C₈ to C₁₅), a distribution of variousalkylbenzenes results from such alkylation. The present invention istherefore in one broad respect concerned with the use of sulfonated2-phenyl alkylbenzenes derived from the alkylation of benzene,preferably using α-mono olefins having a carbon number distribution inthe detergent range, in detergent formulations.

As mentioned above, a 2-phenyl alkylbenzene is but one possiblestructural isomer resulting from the alkylation of benzene with anolefin, and a mixture of 2-phenyl alkylbenzenes results from thealkylation of benzene using as reactants a feed which includes a mixtureof olefins in the detergent range. This may be due to resonancestabilization which permits effective movement of the double bond in anactivated olefin/Lewis acid complex. Generally speaking, the collectionof all isomeric products produced from the alkylation of benzene with amixture of olefins in the detergent range is commonly referred to bythose of ordinary skill in the art as “linear alkylbenzenes”, or“LAB's”. Frequently, those skilled in the art use “linear alkylbenzenes”or “LAB's” interchangeably with their sulfonates. It is common forpeople to say LAB's when they are actually referring to sulfonated LAB'suseful as detergents.

Typically, LAB's are manufactured commercially using classicFriedal-Crafts chemistry, employing catalysts such as aluminum chloride,or using strong acid catalysts such as hydrogen fluoride, for example,to alkylate benzene with olefins. While such methods produce highconversions, the selectivity to the 2-phenyl isomer in such reactions asknown in the prior art is low, generally being about 30% or less. LAB'swith a high percentage of the 2-phenyl isomer are highly desired becausesuch compounds when sulfonated have long “tails” which provide enhancedsolubility and detergent properties.

SUMMARY OF THE INVENTION

In one aspect the present invention provides a method and catalyst forLAB production having high substrate olefin conversion, high selectivityto 2-phenyl isomer LAB production, and employing a catalyst having longlifetimes and easy handling. Through use of this aspect of theinvention, 2-phenyl alkylbenzenes may be produced in yields in excess of80.0% on the basis of catalyst selectivity.

More importantly, the present invention provides detergent compositionsand cleaning formulations made with a component that comprises a mixtureof sulfonated alkylbenzenes in which the hydrocarbon groups that arebonded to the benzene ring may comprise any number of carbon atoms inthe detergent range and in which at least 80% (weight basis) of thesulfonated alkylbenzene isomers present have the phenyl group attachedto the hydrocarbon group in the 2 position of the hydrocarbon group. Theinvention provides detergent compositions and formulations which areformed from an alkylbenzene sulfonate component that comprises a mixtureof: 1) a first alkylbenzene sulfonate component comprising 2-phenylalkylbenzene sulfonates in which 2-phenyl alkylbenzene sulfonate isomerscomprise at least 80% of all alkylbenzene sulfonate isomers present; and2) a second alkylbenzene sulfonate component comprising either: a)alkylbenzene sulfonates in which isomers having the benzene ringattached to a linear alkyl group at a position other than the alkylgroup's 2 position comprise at least 70% of all alkylbenzene sulfonateisomers present; or b) branched alkylbenzene sulfonates, or acombination thereof.

Branched alkylbenzene sulfonates may be introduced into a formulatedproduct according to the invention in one of two ways. First, a portionof the linear olefin feedstock used in the alkylation reaction of thebenzene ring may be replaced by branched olefin(s), to provide analkylbenzenes mixture for sulfonation in which the alkylbenzenes containa selected amount of branched alkylate. The second method of providingbranched alkylbenzene sulfonates in a finished formulation according tothe invention is when branched alkylbenzene sulfonates purchased on theopen market are used as a blending component in the production of afinished product according to the invention. Thus, by either blending orproviding branching in the alkylation reaction product, it is possibleto provide a wide range of the amount of branched alkylbenzenesulfonates in a finished formulation according to the invention;however, it is preferable that the branched isomers comprise any amountless than 50.0% of the total alkylbenzene sulfonate isomers present in agiven formulation according to the invention, in another preferred formof the invention, branched isomers comprise any amount less than 15.00%of the total alkylbenzene sulfonate isomers present in a givenformulation according to the invention; in yet another preferred form ofthe invention, branched isomers comprise any amount less than 2.00% ofthe total alkylbenzene sulfonate isomers present in a given formulationaccording to the invention.

In one preferred form of the invention, lower activity isomers (isomersother than the 2-phenyl isomers) of linear alkylbenzenes are present inthe second alkylbenzene sulfonate component in any amount between 0.00%and 70.00%, including every hundredth percentage therebetween, by weightbased upon the total weight of the second alkylbenzene sulfonatecomponent.

In a preferred form of the invention, the second alkylbenzene sulfonatecomponent may comprise alkylbenzene sulfonates in which isomers havingthe benzene ring attached to a linear alkyl group at a position otherthan the alkyl group's 2 position comprise at least 50% of allalkylbenzene sulfonate isomers present.

In another preferred form of the invention, the second alkylbenzenesulfonate component may comprise alkylbenzene sulfonates in whichisomers having the benzene ring attached to a linear alkyl group at aposition other than the alkyl group's 2 position comprise at least 40%of all alkylbenzene sulfonate isomers present.

In another preferred form of the invention, the second alkylbenzenesulfonate component may comprise alkylbenzene sulfonates in whichisomers having the benzene ring attached to a linear alkyl group at aposition other than the alkyl group's 2 position comprise at least 30%of all alkylbenzene sulfonate isomers present.

Thus, an alkylbenzene sulfonate component according to yet anotherembodiment of the invention may contain sulfonated 2-phenylalkylbenzenes in an amount of at least 30.00% by weight based upon thetotal weight of the sulfonated alkylbenzene component. In another formof the invention, an alkylbenzene sulfonate component may containsulfonated 2-phenyl alkylbenzenes in an amount of at least 40.00% byweight based upon the total weight of the sulfonated phenyl alkylbenzenecomponent. In yet another form of the invention, an alkylbenzenesulfonate component may contain sulfonated 2-phenyl alkylbenzenes in anamount of at least 50.00% by weight based upon the total weight of thesulfonated phenyl alkylbenzene component. In yet another form of theinvention, an alkylbenzene sulfonate component may contain sulfonated2-phenyl alkylbenzenes in an amount of at least 60.00% by weight basedupon the total weight of the sulfonated phenyl alkylbenzene component.In yet another form of the invention, an alkylbenzene sulfonatecomponent may contain sulfonated 2-phenyl alkylbenzenes in an amount ofat least 70.00% by weight based upon the total weight of the sulfonatedphenyl alkylbenzene component. In yet another form of the invention, analkylbenzene sulfonate component may contain sulfonated 2-phenylalkylbenzenes in an amount of at least 80.00% by weight based upon thetotal weight of the sulfonated phenyl alkylbenzene component.

By admixture with conventional mixtures of sulfonated linearalkylbenzene detergents, a mixture of sulfonated alkylbenzenes useful ascomponents in detergent formulations having any desired 2-phenylalkylbenzene isomer content in the range of between about 18.00% and82.00%, including every hundredth percentage therebetween, may beproduced using the materials provided according to the invention. Suchmixtures of sulfonated alkylbenzenes are useful as a component informing detergent and cleaning compositions useful in a wide variety ofapplications as later illustrated in the examples.

It has also been found that a catalyst according to this invention maybe used in combination with an existing aluminum chloride or hydrogenfluoride alkylation facility to afford LAB having a higher 2-phenylisomer content than would otherwise be available from such plant usingconventional catalysts. Thus, an existing facility may be retrofitted toinclude one or more reactors containing the fluorine-containingmordenite of this invention. In this manner, a slip stream of reactantsmay be sent to the mordenite with effluent therefrom being introducedback into the conventional alkylation system. This embodiment hasseveral advantages. For example, the cost of capital is minimized sinceconventional equipment will already be in place. Also, the retrofittedplant can produce higher 2-phenyl isomer LAB at the discretion of itsoperator, depending on need. That is, the plant need not producestrictly high 2-phenyl isomer LAB and can instead produce high 2-phenylisomer at its discretion. In one embodiment, a slip stream of reactantis drawn and sent to one or more reactors containing fluorine-containingmordenite catalyst. The effluent from the fluorine-containing mordenitereactor may then be combined with effluent from the HF or aluminumchloride reactor to provide a product having a higher level of 2-phenylisomer LAB than would otherwise be present in product from an HF oraluminum chloride reactor.

The invention, in one broad respect, is directed at cleaningformulations designed to cleanse a wide variety of surfaces orsubstrates and which possess increased tolerance to water hardness,wherein the formulations comprise an alkylbenzene sulfonate componenthaving a much higher 2-phenyl isomer content than formulationspreviously available commercially, and other components known to beuseful in formulating soaps, detergents, and the like.

The invention, in another broad respect is a process useful for theproduction of mono-alkylbenzene, comprising: contacting benzene with anolefin containing from about 8 to about 30 carbons in the presence offluorine-containing mordenite under conditions such that linearmonoalkylbenzene is formed.

In another broad respect, this invention is a process for the productionof linear alkylbenzene, comprising: a) contacting benzene and an olefinhaving about 8 to about 30 carbons in the presence of afluorine-containing mordenite to form a first linear alkylbenzenestream; b) contacting benzene and an olefin having about 8 to about 30carbons in the presence of a conventional linear alkylbenzene alkylationcatalyst to form a second linear alkylbenzene stream; and c) combiningthe first linear alkylbenzene stream and the second linear alkylbenzenestream form a third linear alkylbenzene stream, as well as the productmade from this process.

In another broad respect, this invention is a process useful for theproduction of linear alkylbenzene, comprising: combining a product froma conventional linear alkylbenzene alkylation reactor with a productfrom a linear alkylbenzene alkylation reactor containingfluorine-containing mordenite.

In yet another broad respect, this invention is a process for theproduction of linear alkylbenzene, comprising: a) dehydrogenating aparaffin to form an olefin; b) sending a primary feed stream of benzeneand the olefin through a conduit to a conventional linear alkylbenzenealkylation reactor; c) contacting the primary feed stream in theconventional linear alkylbenzene alkylation reactor with a conventionallinear alkylbenzene alkylation catalyst under conditions effective toreact the benzene and olefin to form a first linear alkylbenzeneproduct; d) withdrawing a portion of the primary feed stream from theconduit and contacting the portion with a fluorine-containing mordeniteunder conditions effective to react the benzene and olefin to form asecond linear alkylbenzene product; e) combining the first and secondlinear alkylbenzene products to form a crude linear alkylbenzene stream;and f) distilling the crude linear alkylbenzene stream in a firstdistillation column to separate benzene that did not react and to form abenzene-free linear alkylbenzene stream.

Such process may optionally include the steps of: g) distilling thebenzene-free linear alkylbenzene stream in a second distillation columnto separate any olefin and to form a linear alkylbenzene stream; and h)distilling the second olefin free alkylbenzene stream in a thirddistillation column to provide an overhead of a purified linearalkylbenzene product and removing a bottoms stream containing anyheavies.

In another broad respect, this invention is a process useful for theproduction of monoalkylbenzene, comprising: introducing a feedcomprising olefin having about 8 to about 30 carbons and benzene into afluorine-containing mordenite catalyst bed under conditions such thatmonoalkylbenzene is produced, allowing benzene, olefin, andmonoalkylbenzene to descend (fall) into a reboiler from the catalystbed, removing monoalkylbenzene from the reboiler, and heating thecontents of the reboiler such that benzene refluxes to further contactthe fluorine-containing mordenite.

In yet another broad aspect, this invention relates to mordenite usefulfor alkylating benzene with olefin having a silica to alumina molarratio of about 10:1 to about 100:1; wherein the mordenite has beentreated with an aqueous hydrogen fluoride solution such that themordenite contains from about 0.1 to about 4 percent fluorine by weight.

In yet another broad respect, the invention relates to a chemicalmixture that contains linear alkylbenzenes produced using theprocess(es) and/or catalyst(s) taught herein; which chemical mixture isuseful for producing a mixture of sulfonated linear alkylbenzenes whichmixture contains a higher concentration of sulfonated 2-phenylalkylbenzenes than previously available using prior art methods andcatalysts.

In another broad respect, the invention comprises formulations forfinished consumer and industrial strength compositions useful in or as:all-purpose cleaners, pine oil microemulsions, liquid dishwashing soaps,enzyme-based powdered laundry detergents, enzyme-free powdered laundrydetergents, and the like, as it has been found that the use ofsulfonated LAB mixtures having a higher content of the 2-phenyl isomerwith respect to what has been heretofore available from the teachings ofthe prior art improves the effectiveness and cleaning action of allcleaning compositions which contain conventional sulfonated alkylbenzenedetergents, be they linear or branched.

In another broad respect, the invention is a method useful for thepreparation of fluorine-containing mordenite, comprising contacting amordenite having a silica to alumina molar ratio in a range from about10:1 to about 100:1 with an aqueous hydrogen fluoride solution having aconcentration of hydrogen fluoride in the range of from about 0.1 toabout 10 percent by weight such that the mordenite containing fluorineis produced, collecting the fluorine-containing mordenite by filtration,and drying.

The fluorine treated mordenite catalyst advantageously produces highselectivities to the 2-phenyl isomer in the preparation of LAB,generally producing selectivities of about 70 percent or more. Also, thefluorine treated mordenite enjoys a long lifetime, preferablyexperiencing only a 25 percent or less decrease in activity after 400hours on stream. A process operated in accordance with the apparatusdepicted in FIGS. 1 and 2 has the advantage that rising benzene from thereboiler continuously cleans the catalyst to thereby increase lifetimeof the catalyst. In addition, this invention advantageously producesonly low amounts of dialkylbenzene, which is not particularly as usefulfor detergent manufacture, as well as only low amounts of tetralinderivatives.

In another aspect the invention provides solid salts of alkylbenzenesulfonates, which solid salts may contain various cations for chargebalance.

In another aspect the invention comprises finished detergentcompositions useful for cleaning fabrics, dishes, hard surfaces, andother substrates that is formed from components comprising: a) analkylbenzene sulfonate surfactant component present in any amountbetween 0.25% and 99.50% by weight based upon the total weight of thefinished detergent composition, said component characterized ascomprising any amount between 26.00% and 82.00% by weight based upon thetotal weight of the component, and including every hundredth percentagetherebetween, of water-soluble sulfonates of the 2-phenyl isomers ofalkylbenzenes described by the general formula:

wherein n is equal to any integer between 4 and 16; and b) any amountbetween 0.50% and 99.75% of other components known to be useful informulating soaps, detergents, and the like, wherein at least one ofsaid other components is selected from the group consisting of: fattyacids, alkyl sulfates, an ethanolamine, an amine oxide, alkalicarbonates, water, ethanol, isopropanol, pine oil, sodium chloride,sodium silicate, polymers, alcohol alkoxylates, zeolites, perboratesalts, alkali sulfates, enzymes, hydrotropes, dyes, fragrances,preservatives, brighteners, builders, polyacrylates, essential oils,alkali hydroxides, ether sulfates, alkylphenol ethoxylates, fatty acidamides, alpha olefin sulfonates, paraffin sulfonates, betaines,chelating agents, tallowamine ethoxylates, polyetheramine ethoxylates,ethylene oxide/propylene oxide block copolymers, alcohol ethyleneoxide/propylene oxide low foam surfactants, methyl ester sulfonates,alkyl polysaccharides, N-methyl glucamides, alkylated sulfonateddiphenyl oxide, and water soluble alkylbenzene sulfonates having a2-phenyl isomer content of less than 26.00%.

The mordenite catalyst of the present invention is useful as a catalystin the production of LAB's in accordance with the process ofmanufacturing LAB's of this invention. LAB is useful as startingmaterial to produce sulfonated LAB, which itself is useful as asurfactant.

Certain terms and phrases have the following meanings as used herein:

“Meq/g” means milliequivalents of titratable acid per gram of catalyst,which is a unit used to describe acidity of the catalysts. Acidity isgenerally determined by titration with a base, as by adding excessivebase, such as sodium hydroxide, to the catalyst and then back titratingthe catalyst.

“Conv.” and “Conversion” mean the mole percentage of a given reactantconverted to product. Generally, olefin conversion is about 95 percentor more in the practice of this invention.

“Sel.” and “Selectivity” mean the mole percentage of a particularcomponent in the product. Generally, selectivity to the 2-phenyl isomeris about 70% or more in the practice of this invention.

“Detergent range” means a molecular species which contains an alkylgroup that comprises any number of carbon atoms: 8, 9, 10, 11, 12, 13,14 or 15 per alkyl group, and includes LAB, LAB sulfonates, andmono-olefins.

“Substantially linear” when referring to a hydrocarbon or alkyl chainthat is part of an alkylbenzene, whether the alkylbenzene is sulfonatedor not, means a hydrocarbon comprising between 7 and 16 carbon atomslinked to one another to form a straight chain, wherein the carbon atomsof said straight chain may have only hydrogen atoms or a methyl groupbonded to them as appendages.

“Branched alkyl” when referring to a hydrocarbon or alkyl chain that ispart of an alkylbenzene, whether the alkylbenzene is sulfonated or not,means a hydrocarbon comprising between 4 and 16 carbon atoms linked toone another to form a straight chain, wherein one or more of the carbonatoms of said straight chain may have a hydrogen atom and any alkylgroup other than a methyl group (including without limitation ethyl,propyl and butyl groups), bonded to them as appendages.

“Branched alkylbenzene” means a molecular species which comprises abranched alkyl chain appended to a benzene ring.

“Branched alkylbenzene sulfonate” means a water-soluble salt of abranched alkylbenzene that has been sulfonated.

“2-phenyl alkylbenzenes” means a benzene ring having at least one alkylgroup attached to it, wherein the alkyl group comprises any number ofcarbon atoms between 7 and 16 (including every integral numbertherebetween) linked to one another so as to form a substantially linearchain and wherein the benzene ring is attached the alkyl group at acarbon atom that is adjacent to the terminal carbon of the substantiallylinear chain. Thus, the carbon atom that is attached to the benzene ringhas a methyl group and another alkyl group attached to it in a 2-phenylalkylbenzene.

“Sulfonated 2-phenyl alkylbenzenes” means 2-phenyl alkylbenzenes asdefined above which further comprise a sulfonate group attached to thebenzene ring of a 2-phenyl alkylbenzene as described above, regardlessof the position of the sulfonate group on the ring with respect to thelocation of the alkyl group; however, it is most common and preferredthat the sulfonate group is attached to the benzene ring in thepara-position with respect to the alkyl group.

“LAB” means a mixture linear alkylbenzenes which comprises a benzenering appended to any carbon atom of a substantially linear alkyl chainin the detergent range.

“LAB sulfonates” means LAB which has been sulfonated to include anacidic sulfonate group appended to the benzene rings (thus forming aparent acid), and subsequently rendered to a form more soluble toaqueous solution than the parent acid by neutralization using any ofalkali metal hydroxides, alkaline earth hydroxides, ammonium hydroxides,alkylammonium hydroxides, or any chemical agent known by those skilledin the art to react with linear alkylbenzene sulfonic acids to formwater-soluble linear alkylbenzene sulfonates.

“2-phenyl isomer” means LAB sulfonates of 2-phenyl alkylbenzenes.

All percentages are expressed in terms of weight percent, unlessspecified otherwise.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 shows a representation of a first continuous reactivedistillation column employed in the practice of this invention;

FIG. 2 shows a representation of a second continuous reactivedistillation column employed in the practice of this invention;

FIG. 3 shows a representative process scheme for one embodiment of thisinvention where a conventional LAB alkylation reactor is shown incombination with a fluorine-containing mordenite reactor of thisinvention wherein a slip stream of reactant to the conventional reactoris sent to the mordenite reactor and wherein the flow of high 2-phenylisomer LAB from the mordenite reactor may be adjusted to vary the2-phenyl isomer LAB content of the effluent from the conventional LABalkylation reactor.

FIG. 4 shows another representative process scheme for one embodiment ofthis invention where a first conventional LAB alkylation reactor isshown in combination with a fluorine-containing mordenite reactors ofthis invention wherein a slip stream of reactant to the conventionalreactor is sent to one or both of a pair of mordenite reactor andwherein the effluent from the first LAB alkylation reactor and theeffluent from the one or both mordenite reactors are combined and flowedinto a second conventional LAB alkylation reactor.

DETAILED DESCRIPTION OF THE INVENTION

The catalysts used to prepare the linear alkylbenzenes of this inventionis a fluorine-containing mordenite. Mordenite is a type of zeolite. Thecatalyst of this invention is prepared from hydrogen mordenite(typically having 0.1 percent or less of sodium) having a silica-aluminamolar ratio of from about 10:1 to about 100:1. More typically, thestarting mordenite has a silica/alumina molar ratio of from about 10:1to about 50:1. The starting hydrogen mordenite, which is commonlyavailable commercially, is treated with an aqueous solution of hydrogenfluoride (“HF”) to produce the active, long-life and highly selectivecatalyst of the invention. In the course of such HF treatment, as wellas during subsequent calcination of said HF-treated mordenite, thesilica/alumina molar ratio typically increases. The finished catalystsof this invention show a fluorine content of from about 0.1 to about 4percent by weight, more typically about 1 percent.

The aqueous solution used to treat the mordenite may contain a range ofHF concentrations. Generally, the HF concentration is a minimum of about0.1 percent by weight. Below such minimum concentration, the effect ofthe fluorine treatment significantly decreases, resulting in theundesirable need for repeated treatments. Generally, the HFconcentration on the upper end is about 10 percent by weight or less.Above a concentration of about 10 percent by weight, the HF is soconcentrated that it is difficult to prevent HF from destroying thecrystallinity of the mordenite, thereby detrimentally affecting itsefficacy as a catalyst for LAB production.

The aqueous HF solution may be prepared by diluting commerciallyavailable 48% HF solutions to the desired concentration. Alternatively,HF can be sparged into water to provide an aqueous HF solution.

Typically, the treatment is carried out by adding mordenite powder orpellets to a stirred aqueous HF solution at a temperature of from about0° C. to about 50° C. The stirring and contacting is continued for atime sufficient to achieve the desired level of fluorine in themordenite. This time may vary depending on factors such as HFconcentration, amount of HF solution relative to the amount of mordenitebeing treated, speed of agitation is employed, and temperature. Aftertreatment, the mordenite can be recovered by filtration, and then dried.It is also possible to impregnate the mordenite to incipient wetnesswith a given HF solution, as well as to treat the mordenite with gaseoushydrogen fluoride. Preferably said fluoride-treated mordenite would becalcined in air prior to use in alkylation service. The preferredcalcination temperature would be in the range from about 400° C. toabout 600° C. Alternative mordenite fluorinating agents to hydrofluoricacid and hydrogen fluoride include ammonium fluoride, fluorided siliconcompounds and fluorided hydrocarbons.

The HF-treated mordenite of this invention generally has about 0.1percent by weight or more of fluorine based on the total weight of themordenite. Typically, the fluorine-containing mordenite contains about 4percent by weight or less fluorine. The fluorine-containing mordenitemost typically contains about 1 percent by weight of fluorine.

The mordenite can be used in the practice of this invention as a powder,in pellet form, as granules, or as extrudates. The mordenite can beformed into pellets or extrudates using binders well known to those ofskill in the art, such as alumina, silica or mixtures thereof.

Reactants for LAB Production

In the practice of this invention, benzene is alkylated with olefin toform LAB. These reactants can be handled and purified as is generallyperformed by those of ordinary skill in the art. In this regard, it ispreferred that the reactants are water and alcohol free The olefinsemployed in the practice of this invention have from about 8 to about 30carbons, preferably from about 10 to about 14 carbons, such as isavailable commercially or produced as dehydrogenated paraffin feedstocks. It is preferred that the olefin be mono unsaturated. It is mostpreferred that the olefin be an alpha-olefin containing a terminalethylene unit.

Olefins in the 10 to 14 carbon number range are typically available fromthe dehydrogenation of a C₁₀ to C₁₄ paraffin mixture using methods knownto those skilled in the art. Dehydrogenation of such paraffins providesa mixture of mono-olefins having a double bond at the terminal carbon inthe chain and its neighboring carbon atom, and leaves some of theparaffins unconverted. Thus, the effluent of a dehydrogenation reactorinto which was fed a C₁₀ to C₁₄ mixture typically comprises a mixturewhich is predominantly paraffins and has an olefin content of about 5 to20%, and is readily available. Often, the olefin content of saidolefin-paraffin mixture may be 8 to 10 weight %.

The process of this invention for producing the 2-phenyl isomer of theLAB having the formula previously set forth above can be carried outusing the continuous reactive distillation column depicted in FIG. 1. InFIG. 1, a feed mixture of benzene and olefin, generally at abenzene-to-olefin molar ratio range of about 1:1 to 100:1 flows fromfeed pump 10 to feed inlet 14 via line 12. The feed mixture falls topacked mordenite catalyst bed 32 where alkylation in the presence of thefluorine-containing mordenite occurs. Alternatively, while not depictedin FIG. 1, the benzene and olefin can be introduced separately into thebed with mixing occurring in the bed, or the reactants can be mixed viaan in-line mixer prior to introducing the reactants into the catalystbed, or the reactants can be injected separately above the bed withmixing affected by use of standard packing above the bed, or thereactants can be sparged into the chamber above the bed. The catalystbed 32 depicted in FIG. 1 for laboratory scale may be made of twolengths of 1.1 inch internal diameter tubing, the lengths being 9.5inches and 22 inches. In the catalyst bed 32, the falling feed mixturealso contacts rising vapors of unreacted benzene which has been heatedto reflux in reboiler 42 by heater 40. Such rising vapors pass overthermocouple 38 which monitors temperature to provide feedback to heater40. The rising vapors of benzene and/or olefin also pass throughstandard packing 36 (e.g., 7.5 inches of goodloe packing). The risingvapors heat thermocouple 30 which connects to bottoms temperaturecontroller 28 which activates heater 40 when temperature drops below aset level.

Prior to startup, the system may be flushed with nitrogen which entersvia line 54 and which flows through line 58. After startup, a nitrogenblanket is maintained over the system. Also prior to startup and duringnitrogen flush, it may be desirable to heat catalyst bed 32 so as todrive off water from the fluorine-containing mordenite.

Residual water from the feed mixture or which otherwise enters thesystem is collected in water trap 24 upon being liquefied at condenser21 (along with benzene vapor). If the feed is very dry (free of water)the water trap 24 may not be needed. Removing water leads to longercatalyst lifetime. Hence, the water trap 24 is optional. The sameapplies to FIG. 2. Condenser 21 is cooled via coolant such as waterentering condenser 21 via port 22 and exiting via port 20. As needed,water in water trap 24 may be drained by opening drain valve 26.

As needed, when LAB content in reboiler 42 rises to a desired level, thebottoms LAB product may be removed from the system via line 47, usingeither gravity or bottoms pump 48 to withdraw the product. When productis so withdrawn, valve 44 is opened.

In FIG. 1, dip tube 46, which is optional, is employed to slightlyincrease the pressure in reboiler 42 to thereby raise the boiling pointof benzene a degree or two. Likewise, a pressure generator 56 may beoptionally employed to raise the pressure of the system. Other standardpressure increasing devices can be employed. Pressure can thus beincreased in the system such that the boiling point of benzene increasesup to about 200° C.

In FIG. 1, control mechanisms for heat shutoff 50 and pump shutoff 52are depicted which serve to shut off heat and pump if the liquids levelin the system rises to such levels. These control mechanisms areoptional and may be included so that the catalyst bed does not come intocontact with the bottoms of the reboiler. Line 60 connects pump shutoff52 to the system above condenser 21.

In the practice of this invention in the alkylation of benzene, a widevariety of process conditions can be employed. In this regard, thetemperature in the catalyst bed may vary depending on reactants, rate ofintroduction into the catalyst bed, size of the bed, and so forth.Generally, the bed is maintained at the reflux temperature of benzenedepending on pressure. Typically, the temperature of the catalyst bed isabove about 70° C., and most likely about 78° C. or more in order tohave reasonable reaction rates, and about 200° C. or less to avoiddegradation of reactants and products and to avoid deactivation of thecatalyst by coke build-up. Preferably, the temperature is in the rangefrom about 80° C. to about 140° C. The process may be operated at avariety of pressures during the contacting step, with pressures of aboutatmospheric most typically being employed. When the process is operatedusing a system as depicted in FIGS. 1 and 2, the reboiler temperature ismaintained such that benzene and olefin vaporize, the temperaturevarying depending on olefin, and generally being from about 80° C. toabout 250° C. for olefins having 10 to 14 carbons. The composition ofthe reboiler will vary over time, but is generally set initially to havea benzene olefin ratio of about 5:1, with this ratio being maintainedduring the practice of this invention. The rate of introduction of feedinto the catalyst bed may vary, and is generally at a liquid hourlyspace velocity (“LHSV”) of about 0.05 hr⁻¹ to about 10 hr⁻¹, moretypically from about 0.05 hr⁻¹ to about 1 hr⁻¹. The mole ratio ofbenzene to olefin introduced into the catalyst bed is generally fromabout 1:1 to about 100:1. In commercial benzene alkylation operations,it is common to run at mole ratios of from about 2:1 to about 20:1,which can suitably be employed in the practice of this invention, and tocharge said olefins as an olefin-paraffin mixture comprising 5% to 20%olefin content. Said olefin-paraffin mixtures are normally generatedcommercially through dehydrogenation of the corresponding paraffinstarting material over a noble metal catalyst.

Another continuous reactive distillation apparatus is depicted in FIG.2. In FIG. 2, the feed mixture enters the reactor via feed inlet 114.The feed mixture falls through the column into catalyst bed 132, whereinalkylation to form LAB occurs. A thermowell 133 monitors the temperatureof said catalyst bed 132. The catalyst bed 132 may be optionally heatedexternally and is contained within 1¼ inch stainless steel tubing.Goodloe packing is positioned at packing 136 and 137. LAB product, aswell as unreacted benzene and olefin, fall through packing 136 intoreboiler 142. In reboiler 142, electric heater 140 heats the contents ofreboiler 142 such that heated vapors of benzene and olefin rise from thereboiler 142 to at least reach catalyst bed 132. As needed, the bottomsLAB product may be removed from reboiler 142 by opening bottoms valve144 after passing through line 147 and filter 145. Residual water fromthe feed mixture, or which otherwise enters the system, may be condensedat condenser 121 which is cooled with coolant via outlet line 122 andinlet line 120. The condensed water falls to water trap 124, which canbe drained as needed by opening drain valve 126. Temperature in thesystem is monitored via thermocouples 138, 130, and 165. The systemincludes pressure release valve 166. A nitrogen blanket over the systemis maintained by introduction of nitrogen gas via inlet line 154. Levelcontrol activator 150 activates bottoms level control valve 151 to openwhen the liquids level in the reboiler rises to the level controlactivator 150. Line 160 connects level control activator 150 to thesystem above condenser 121.

While the systems depicted in FIG. 1 and FIG. 2 show single catalyst bedsystems, it may be appreciated that multi-catalyst bed reactors arewithin the scope of this invention, as well as multiple ports for inletfeeds, water traps, product removal lines, and so forth. Moreover, theprocess may be run in batch mode, or in other continuous processes usingplugflow designs, trickle bed designs, and fluidized bed designs.

It is believed that as average molecular weight of olefins increases,particularly when the average number of carbons exceed 14, theselectivity and conversion to LAB, especially LAB with the 2-isomer, mayincrementally decrease. If desired, the product of the alkylation usingHF-treated mordenite may be sent to a second, finishing catalyst bed toimprove yield. This procedure is optional and is believed to bedependent on the needs and desires of the end user. An example of such asecond catalyst is HF-treated clay such as montmorillonite clay havingabout 0.5% fluoride. Such a catalyst may also serve to lower the brominenumber below about 0.1, depending on conditions.

Variable 2-Phenyl Isomer Content of Product Using the Mordenite of theInvention in Combination with Conventional LAB Alkylation

The fluorine-containing mordenite of this invention generally producesLAB having high 2-phenyl isomer content, such as higher than about 70%.Currently, LAB purchasers who make detergents would prefer to use LABhaving a 2-phenyl isomer content in the range from about 30 to about 40percent, but this level is not available in the marketplace.Conventional LAB alkylation technology do not achieve these higher2-phenyl isomer levels. HF, which is currently the most widely usedcatalyst for production of LAB on a commercial scale, produces about16-18 percent of the 2-phenyl isomer in the product stream from thereactor. Aluminum chloride, in contrast, produces about 26-28 percent ofthe 2-phenyl isomer. The present inventors recognized that a need existsfor a process which produces a 2-phenyl isomer product in the desiredrange.

It has now been found that the mordenite of this invention can be usedin combination with conventional LAB alkylation catalysts, such as HFand aluminum chloride alkylation catalysts. This may be affected bywithdrawing a slip stream of reactant that is being sent to theconventional LAB reactor, and directing the slip stream to the mordenitereactor. Since conventional LAB catalysts produce product having a2-phenyl isomer content much less than that from mordenite of thisinvention, combining the products from each catalyst results in aproduct having a higher 2-phenyl isomer content than that from theconventional LAB alkylation catalyst. For example, while the catalyst ofthis invention typically produces a 2-phenyl isomer content of 70% ormore, a typical HF process produces about 16-18% of the 2-phenyl isomer.By combining effluent from each catalyst at given proportions, theresulting mixture will have any desired 2-phenyl isomer content in therange between the 2-phenyl isomer contents of the HF catalyst productand the mordenite catalyst product. Thus, the levels of 2-phenyl isomermay be adjusted by the amount of reactants sent to the mordenitecatalyst and/or by storing 2-phenyl isomer product from the mordenitecatalyst for later mixing with the product of from the conventional LABalkylation catalyst to thereby achieve any desired level of 2-phenylisomer content in the final product. An advantage of this inventionpertains to the ability to retrofit an existing, conventional LAB systemwith a reactor containing fluorine-treated mordenite of this invention.This enables existing users of the conventional LAB technology toaugment their existing facilities without interrupting their production.This provides a considerable cost advantage to the producer.

The conventional LAB catalysts used most frequently are HF alkylationreactors and aluminum chloride alkylation catalysts. Other alkylationcatalysts include various zeolites, alumina-silica, various clays, aswell as other catalysts.

FIG. 3 depicts a representative, non-limiting scheme for practice ofthis invention wherein the fluorine-treated mordenite is used incombination with a HF alkylation reactor to afford LAB having high2-phenyl isomer contents relative to that produced from the HF reactoralone. The scheme of FIG. 3 is shown in the context of LAB alkylationbased on a feed from a paraffin dehydrogenation facility. Prior to thisinvention, the plant depicted in FIG. 3 would be operated conventionallywithout use of mordenite reactor 220.

Thus, in conventional operation, fresh paraffin is fed to conventionaldehydrogenation apparatus 210 via line 211, with recycled paraffin beingintroduced from the paraffin column 250 via line 252. Dehydrogenatedparaffin from the dehydrogenation apparatus 210 is then pumped into aconventional alkylation reactor 230 containing conventional LABcatalyst, such as HF, via conduit 214. The dehydrogenated paraffin feedmay of course be supplied from any provider. The source ofdehydrogenated paraffin (olefin) is not critical to the practice of thisinvention. LAB product from alkylation unit 230 may thereafter bepurified by a series of distillation towers.

In this regard, alkylation effluent is delivered to a benzene column 240by way of line 231. It should be appreciated that the alkylation productmay be sent offsite for purification. Further, the particularpurification scheme used is not critical to the practice of thisinvention, but is depicted in FIG. 3 as representative of a typicalcommercial operation. In FIG. 3, unreacted benzene is distilled off fromthe crude LAB product. Benzene is then recycled to the alkylationreactor 230. The benzene-free LAB crude product from the benzene column240 is pumped through line 241 to paraffin column 250 where any paraffinpresent is distilled off, with the distilled paraffin being recycled toparaffin dehydrogenation unit 210 via line 252. Paraffin-free crude LABalkylate from the paraffin column 250 is transported to a refiningcolumn 260 where purified LAB is distilled and removed via line 262.Heavies (e.g., dialkylates and olefin derivatives) are withdrawn fromrefining column 260 via conduit 261.

In the practice of this invention, a fluorine-treated mordenitecontaining reactor 220 is used in conjunction with the conventionalalkylation reactor 230. In the embodiment of this invention depicted inFIG. 3, a slip stream of benzene/dehydrogenated paraffin feed is takenfrom line 214 and pumped through mordenite reactor 220 where high2-phenyl isomer production is achieved. LAB product from reactor 220,high in 2-phenyl isomer, is then introduced back into line 214 via line222. Alternatively mordenite reactor 220 may be fed benzene anddehydrogenated paraffin (olefin) directly, rather than by way of a slipstream from line 221. In addition, effluent from reactor 220 may, in thealternative if no unreacted olefin is present, be sent directly tobenzene column 240, for later combination with conventional alkylationreactor 230 product or transported and tied into conduit 231, whichfeeds benzene column 240. It should be appreciated that columns 240,250, and 260 may be maintained at conditions (e.g., pressure andtemperature) well known to those of skill in the art and may be packedwith conventional materials if desired.

FIG. 4 depicts an alternative configuration to that shown in FIG. 3. InFIG. 4, dual mordenite beds 320, 321 are used in conjunction withconventional alkylation reactors 330, 340. Conveniently, one of themordenite reactors may be in operation while the other reactor is downfor catalyst regeneration. For example, during operation, olefin feed(dehydrogenated paraffin) is supplied via line 301, with benzene orother aromatic feed stock being provided via line 302. The admixedreactants may flow to standard alkylation reactor 330 via line 304 bafter passing through heat exchanger 303. A portion of the mixed streammay be withdrawn via line 304 a for supply to the mordenite reactor. Theextent of the mixed feed stream being withdrawn may be varied dependingon the desired level of 2-phenyl isomer in the final product. In anotherembodiment, the product from the reactor containing mordenite 320, 321may be fed to the first alkylation reactor 330, particularly if thesecond alkylation reactor 34 is not employed in the process.

The slip stream reactants may optionally be sent to dewatering unit 317by application of pump 306 after passing through heat exchanger 305. Inthe dewatering unit 317, water is distilled from the reactants indewatering tower 310. Rising vapor exits via line 311 a and passesthrough heat exchanger 312 wherein condensation occurs. Effluent fromheat exchanger 312 is advanced to water trap 318 via line 311 b. Wateris removed from water trap 318 via line 313, with the bottom organiclayer being returned to the dewatering tower 310. Dewatered reactantsmay be removed via line 316 and conveyed to either line 316 a or line316 b. Some of the dewatered reactant may be withdrawn by conduit 314 b,sent through heat exchanger 315 and returned to the tower 310 via line314 a. In this regard, heat exchanger 315 may serve as a reboiler.

After reaction in either reactor 320 or 321, LAB product is sent tolines 322 and 331 from either line 322 a or 322 b after passing throughheat exchanger 323. When desired, one of the catalyst beds may beregenerated, as by calcination for example, through use of regenerationheater 350, which may be connected to the reactor of choice by dottedline 351 through valving and hardware that are not shown. The reactors320 and 321 may optionally be run simultaneously. The reactors 320 and321 may be loaded with mordenite catalyst in any fashion, as would beapparent to one of skill in the art. Typically, a plugged flowarrangement is used. The amount of catalyst employed may vary dependingon a variety of considerations such as type and flow rate of reactants,temperature and other variables. The combined effluents fromconventional reactor 330 and mordenite reactors 320 or 321 may be fed toa second conventional reactor 340, or optionally may be sent to apurification section directly if no unreacted olefin is present (theconventional reactor serves to complete reaction of any olefin that isnot converted in the mordenite reactors 320, 321). In FIG. 4, effluentfrom the second conventional alkylation reactor is advanced to apurification section. The second alkylation reactor may be used to reactunreacted feed stock from reactors 330, 320 and 321 to thereby reducerecycle loads.

It should be appreciated that a wide variety of configurations arecontemplated, and the figures should not be construed as limiting thisinvention or claims hereto. Additional reactors and other equipment may,for example, be used.

The following examples are illustrative of the present invention and arenot intended to be construed as limiting the scope of the invention orthe claims. Unless otherwise indicated, all percentages are by weight.In the examples, all reactants were commercial grades and used asreceived. The apparatus depicted in FIG. 1 was employed for examples2-4. The apparatus depicted in FIG. 1 was used for example 5.

It may be noted that example 2 illustrates LAB production from paraffindehydrogenate using the fluoride-treated mordenite catalyst of exampleB, where good catalyst life (250+ hrs) is achieved without catalystregeneration, while maintaining a 2-phenyl isomer selectivity of >70%and high LAB productivity without significant loss of fluoride.Comparative example 1, on the other hand, using untreated mordenite,with no fluoride added, shows a rapid decline in LAB production. Inaddition, examples 3 and 4 illustrate LAB production using a 5:1 molarbenzene/C₁₀-C₁₄ olefin feed mix and the fluoride-treated mordenitecatalysts of Example B when operating at different LHSV's in the rangeof 0.2-0.4 hr⁻¹. Catalyst life may exceed 500 hours. Example 5illustrates LAB production with the fluoride-treated mordenite catalystwhere the alkylation is conducted at higher temperatures and underpressure. Examples 6-8 illustrate the performance of three HF-treatedmordenite catalysts with different fluoride loadings. Example 9 showshow virtually no alkylation activity is observed with ahighly-fluorinated mordenite.

EXAMPLE A

This example illustrates the preparation of a hydrogen fluoride-modifiedmordenite.

To 30 g of acidified mordenite (LZM-8, SiO₂/Al₂O₃ ratio 17; Na₂O wt %0.02, surface area 517 m²/g, powder, from Union Carbide Corp.) was added600 ml of 0.4% hydrofluoric acid solution, at room temperature. After 5hours the solid zeolite was removed by filtration, washed with distilledwater, dried at 120° C. overnight, and calcined at 538° C.

EXAMPLE B

The example illustrates the preparation of a hydrogen fluoride-modifiedmordenite.

To 500 g of acidified, dealuminized, mordenite (CBV-20A from PQ Corp.;SiO₂/Al₂O₃ molar ratio 20; Na₂O, 0.02 wt %; surface area 550 m²/g,{fraction (1/16)}″ diameter extrudates, that had been calcined at 538°C., overnight) was added a solution of 33 ml of 48% HF solution in 1633ml of distilled water, the mix was cooled in ice, stirred on a rotaryevaporator overnight, then filtered to recover the extruded solids. Theextrudates were further washed with distilled water, dried in vacuo at100° C., and then calcined at 538° C., overnight.

Analyses of the treated mordenite showed:

F: 1.2%; Acidity: 0.49 meq/g

EXAMPLE 1

This example illustrates the preparation of linear alkylbenzenes using ahydrogen fluoride-modified mordenite catalyst.

To a 500 ml flask, fitted with condenser and Dean Stark Trap was added100 ml of benzene (reagent grade) plus 10 g of hydrogenfluoride-modified mordenite zeolite, prepared by the method of ExampleA. The mix was refluxed for 15-20 minutes to remove small amounts ofmoisture, then a combination of benzene (50 ml) plus 1-dodecene (10 g)was injected into the flask and the solution allowed to reflux for 3hours.

Upon cooling, the modified mordenite catalyst was removed by filtration,the filtrate liquid flashed to remove unreacted benzene, and the bottomsliquid analyzed by gas chromatography.

Typical analytical data are summarized in Table 1.

TABLE 1 DODECENE LAB ISOMER DISTRIBUTION (%) HEAVIES LINEAR LAB (LLAB)CONV. (%) 2-Ph 3-Ph 4-Ph 5-Ph 6-Ph (%) (%) 99.7 79.9 16.6 0.8 1.3 1.30.2 95.9

EXAMPLE 2

This example illustrates the preparation of linear alkylbenzenes fromparaffin dehydrogenate using a hydrogen fluoride-treated mordenitecatalyst.

In example 2, benzene was alkylated with a sample of C₁₀-C₁₄ paraffindehydrogenate containing about 8.5% C₁₀-C₁₄ olefins. Alkylation wasconducted in a process unit as shown in FIG. 1.

Alkylation was conducted by first charging 500 ml of a benzene/paraffindehydrogenate mix (10:1 molar ratio, benzene/C₁₀-C₁₄ olefin) to thereboiler and 250 cc of the HF-treated mordenite of example B to the 1.1″i.d. reaction zone. The mordenite was held in place using Goodloepacking. The reboiler liquid was then heated to reflux and a benzeneplus C₁₀-C₁₄ paraffin dehydrogenate mix (10:1 molar ratio,benzene/C₁₀-C₁₄ olefin) continuously introduced into the unit above thecatalyst column at the rate of 100 cc/hr. (LHSV=0.4 hr⁻¹).

Under steady state, reflux, conditions liquid product was continuouslywithdrawn from the reboiler and water continuously taken off from thewater trap. The crude liquid product was periodically analyzed by gaschromatography. The reboiler temperature was typically in the controlledrange of 97-122° C. The column head temperature variability was 78-83°C. A summary of the analytical results may be found in Table 2.

After 253 hours on stream, the recovered HF-treated mordenite catalystshowed by analysis: F: 1.1%; Acidity: 0.29 meq/g; H₂O: 0.3%

TABLE 2 Time on Alkylate 2-Phenyl C₆H₆ Stream (Hrs) Sample Conc. (%)Sel. (%) Conc. (%) 0 0 1.4 32.3 2 1 3.4 19.7 4 2 5.8 74.9 16.6 6 3 6.675.8 25.2 32 4 7.9 80.7 27.0 56 5 7.8 82.7 27.0 69 6 7.3 81.4 27.4 94 76.5 82.0 27.8 118 8 6.0 78.4 27.7 142 9 5.9 81.3 26.9 166 10 5.4 81.527.3 207 11 5.3 81.3 26.1 229 12 5.1 81.1 27.4 253 13 4.9 81.4 28.1

COMPARATIVE EXAMPLE 1

This example illustrates the preparation of linear alkylbenzene fromparaffin dehydrogenate using an untreated mordenite catalyst. Followingthe procedures of Example 9, the alkylation unit was charged with 250 ccof untreated, calcined, mordenite, (the starting mordenite of ExampleB), and the liquid feed comprised benzene plus C₁₀-C₁₄ paraffindehydrogenate mix in a 10:1 molar ratio of benzene/C₁₀-C₁₄ olefin.

Typical results are summarized in Table 3.

The recovered mordenite showed by analysis: Acidity: 0.29 meq/g; H₂O:2.1%

TABLE 3 Time on Alkylate 2-Phenyl C₆H₆ Stream (Hrs) Sample Conc. (%)Sel. (%) Conc. (%) 0 0 11.2 2 1 6.50 9.9 4 2 7.16 73.2 17.1 6 3 7.0973.1 26.4 22 4 8.61 73.9 26.6 31 5 10.49 67.4 15.8 46 6 7.39 75.0 27.770 7 6.39 75.1 28.5 93 8 6.08 73.6 23.0 144 9 5.21 73.6 15.8 157 10 4.4073.9 26.2 180 11 3.06 69.6 27.1 204 12 1.32 19.5 228 13 1.32 33.3

EXAMPLE 3

This example also illustrates the preparation of linear alkylbenzenefrom paraffin dehydrogenate using a hydrogen fluoride-treated mordenitecatalyst.

Following the procedures of Example 2, the alkylation unit was chargedwith 250 cc of the HF-treated mordenite of Example B, and the liquidfeed comprised a benzene plus C₁₀-C₁₄ paraffin dehydrogenate mix in a5:1 molar ratio of benzene/C₁₀-C₁₄ olefin, the reboiler temperature wastypically in the range of 122-188° C., the column head temperature78-83° C. Typical analytical results are summarized in Table 4.

After 503 hours on stream, the recovered HF-treated mordenite catalystshowed on analysis: F: 1.0%; Acidity: 0.35 meq/g; H₂O: 0.1%

TABLE 4 Time on Corrected^(a) Stream Alkylate 2-Phenyl C₆H₆ Alkylate(Hrs) Sample Conc. (%) Sel. (%) Conc. (%) Conc. (%) 0 0 1.0 8.9 1.1 2  13.5 61.8 0.3 3.5 4  2 7.1 72.1 0 7.1 6  3 6.8 76.7 7.2 7.3 34  4 8.479.7 14.3 9.8 71  5 7.2 81.8 14.6 8.5 96  6 6.5 80.8 15.5 7.7 119  7 6.380.6 15.1 7.4 643  8 6.0 81.0 14.3 7.0 168  9 5.9 80.7 14.4 6.9 239 105.0 78.2 8.8 5.5 263 11 5.3 79.2 13.5 6.2 288 12 5.0 79.6 16.5 6.0 31113 5.4 79.4 4.1 5.6 335 14 5.5 79.2 8.2 6.0 408 15 4.9 79.4 13.1 5.6 43216 4.7 78.8 14.4 5.5 456 17 4.4 78.5 14.1 5.1 479 18^(a) 4.7 78.62.7^(b) 4.8 488 19^(b) 4.9 78.5 2.4^(c) 5.0 503 20^(b) 5.1 78.9 0.6^(c)5.1 ^(a)Corrected for benzene in effluent sample. ^(b)Applied pressure8″ H₂O ^(c)Applied pressure 12″ H₂O

EXAMPLE 4

This example also illustrates the preparation of linear alkylbenzenesfrom paraffin dehydrogenate using a hydrogen fluoride-treated mordenitecatalyst.

Following the procedures of Example 2, alkylation was conducted in theglassware unit of FIG. 1 complete with catalyst column, reboiler,condenser and controls. To the reaction zone was charged 500 cc ofHF-treated mordenite of Example B. The liquid feed comprised a benzeneplus C₁₀-C₁₄ paraffin dehydrogenate mix in a 5:1 molar ratio ofbenzene/C₁₀-C₁₄ olefin. The feed rate was 100 cc/hr (LHSV:0.2 hr⁻¹).

Under typical steady state, reflux, conditions, with a reboilertemperature range of 131-205° C. and a head temperature of 76-83° C.,typical results are summarized in Table 5.

TABLE 5 Pressure Time on Alkylate Corrected^(a) (Inch Reboiler StreamConc. 2-Phenyl C₆H₆ Conc. Alkylate H₂O) Temp. (C.) (Hrs) Sample (%) Sel.(%) (%) Conc. (%) 12 205  2  1 8.2 74.3 0.5 8.3 193  4  2 9.2 75.0 0.49.2 175  6  3 10.0 74.8 2.3 10.3 204  21  4 12.7 78.7 0.3 12.7 146  44 5 11.7 81.0 10.4 12.9 136  68  6 11.5 81.8 10.0 12.7 2-3 days C^(b)11.6 81.4 9.4 12.7 136  93  7 11.3 82.6 10.8 12.5 4-5 days C-1^(b) 11.081.8 11.0 12.2 142 165  8 10.4 83.0 11.4 11.5 142 189  9 10.2 83.4 10.511.2 146 213 10 9.7 80.2 11.2 10.7 139 238 11 9.6 83.4 11.1 10.7 143 26112 9.9 81.9 11.0 11.0 133 333 13 9.2 83.4 11.3 10.3 138 356 14 8.9 83.511.1 9.9 138 381 15 8.8 83.0 11.3 9.8 131 405 16 8.7 82.8 11.2 9.7^(a)Corrected for benzene in effluent sample ^(b)Composite product

EXAMPLE 5

This example illustrates the preparation of linear alkylbenzenes fromparaffin dehydrogenate using a hydrogen fluoride-treated mordenitecatalyst.

Following the procedures of Example 2, alkylation of benzene withC₁₀-C₁₄ paraffin dehydrogenate was conducted using the stainless-steelunit of FIG. 2, complete with catalyst column, reboiler, condenser, andcontrols. About 250 cc or HF-treated mordenite of Example B was chargedto the column. The liquid feed comprised benzene plus C₁₀-C₁₄ paraffindehydrogenate mix in a 10:1 molar ratio of benzene/C₁₀-C₁₄ olefin. TheLHSV varied from 0.2 to 0.4 hr⁻¹.

Alkylation was conducted over a range of column and reboilertemperatures and a range of exit pressures. Typical results aresummarized in Table 6.

TABLE 6 Pressure Pot. Alkylate 2- C₆H₆ Column DIFF EXIT Temp. TimeSample Conc. Phenyl Conc. Temp (° C.) (psi) (psi) (° C.) (hr) (#) (%)Sel. (%) (%) 149-129 0.1 0 188 4  1 3.8 6.3 152-126 0 0 200 20  2 1.832.7 195-108 0 0 199 25  3 5.7 8.7 218-111 0 0 201 28  4 0.8 67.5212-118 0 0 201 44  5 8.8 71.7 4.5 209-114 0.2 0 198 52  6 2.4 47.3228-116 0 0 197 68  7 6.9 72.6 12.4 187-107 0.5 0 197 76  8 2.9 74.644.1 76   9^(a) 4.8 72.9 25.3  9C^(b) 6.8 72.2 1.0 174-107 0 0 178 6 104.1 79.2 54.9 170-106 0 0 172 22 11 2.0 59.8 28  12^(a) 6.6 76.8 26.8142-107 0 0 136 31 13 4.8 67.9 18.9 141-110 0 0 138 47 14 4.4 65.9 16.9142-110 0 0 136 55 15 5.0 63.9 16.6 168-111 0 0 131 71 16 4.1 64.8 16.7170-108 0 0 150 79 17 5.0 72.0 8.8 175-113 0 0 143 95 18 5.9 68.1 15.2145-106 0 5.2 188 14 19 3.2 60.2 9.0 149-108 0 4.2 186 20 20 4.8 66.312.0 160-118 0 11.7 213 29 21 4.2 6.7 160-119 0 9.3 210 44 22 5.2 6.6^(a)Composite product ^(b)Stripped composite product

EXAMPLES 6-8

These examples illustrate the preparation of linear alkylbenzene usinghydrogen fluoride-modified mordenite catalysts with different fluoridetreatment levels.

Following the procedures of Example 1, the alkylation unit was chargedwith benzene (100 ml), a 10 g sample of hydrogen fluoride-modifiedmordenite prepared by the procedure of Example B, plus a mix of benzene(50 ml) and 1-decene (10 g). Three HF-treated mordenites were tested,having the composition:

Catalyst “C” 0.25% HF on mordenite (CBV-20A)

Catalyst “D” 0.50% HF on mordenite (CBV-20A)

Catalyst “E” 1.0% HF on mordenite (CBV-20A)

In each experiment samples of the bottoms liquid fraction were withdrawnat regular periods and subject to gas chromatography analyses. Theresults are summarized in Table 7.

TABLE 7 CATALYST TIME % LLAB % ISOS % HVY % 2 Ph % 3 Ph % 4 Ph % 5 Ph %6 & 7 Ph D 10 11.75 0.14 0 73.36 21.87 2.89 0.94 1.02 20 12.43 0.21 072.97 21.96 3.14 1.13 0.81 30 12.88 0.21 0 72.67 22.13 3.03 1.16 1.01 4012.27 0.22 0 73.02 21.92 2.85 1.06 1.14 50 12.15 0.98 0 72.46 21.67 3.211.17 1.49 50 12.24 1.01 0 72.53 21.63 3.23 1.12 1.44 60 12.28 0.21 072.96 22.07 2.93 1.14 0.91 60 11.98 0.21 0 72.97 22.21 2.93 1.17 0.83 C10 12.2 0.18 0 72.54 22.46 3.21 0.98 0.82 20 12.7 0.39 0 71.51 22.612.91 1.02 2.13 30 12.52 0.21 0 71.96 22.68 2.96 1.04 1.36 40 12.75 0.210 71.84 22.67 3.22 1.02 1.25 50 12.98 0.21 0 71.57 22.81 3.16 1.08 1.3960 12.54 0.21 0 71.45 22.81 3.19 1.12 1.44 60 12.33 0.21 0 71.61 22.872.92 1.05 1.31 E 10 10.56 0.05 0 75.19 19.41 2.18 3.22 20 12.95 0.15 074.36 19.23 3.01 3.4 30 13.44 0.18 0 74.11 19.42 3.2 3.27 40 13.16 0.150 074.16 19.38 3.12 3.34 50 13.1 0.15 0 74.43 19.16 3.21 3.28 60 12.830.15 0 74.28 19.49 2.88 3.35 60 12.87 0.16 0 73.82 19.97 2.8 3.2

EXAMPLE 9

This example illustrates the inactivity of a heavily loadedhydrogen-fluoride modified mordenite catalyst.

Following the procedures of Example 2, the alkylation unit was chargedwith 100 cc of a hydrogen fluoride-treated mordenite (CBV-20A) preparedby the method of Example B but having a much higher loading of HF(fluoride content 4.8%). The acidity of said HF-treated mordenite was0.15 meq/g.

No significant amount of alkylated product was detected by gaschromatography.

Compositions Having Enhanced Water Hardness Tolerance

A surprising observation of increased water hardness tolerance wasunexpectedly observed when using LAB sulfonates having a high 2-phenylisomer content in various cleaning formulations, as set forth below. Asis well-known to those of ordinary skill in the chemical arts, mostordinary “tap” water contains varying amounts of cations of the alkalineearth metals calcium and magnesium. These metals are well known to formrelatively insoluble complexes (a.k.a. “soap scum”) with most soap anddetergent molecules, including the LAB sulfonate materials of the priorart. Such complexation frequently results in precipitation of the saltsformed by the union of the above-mentioned cations with materialscommonly used as soaps, and such complexation results in precipitationof the complex with an attendant effective decrease of the totalconcentration of detergent in solution. This is an especially troublingproblem in areas such as parts of Texas where the local water supply maycontain as much as 0.10% of calcium and magnesium hardness, which rendersome soaps and detergents essentially useless. To reduce the effects ofhardness, formulators must often add a chelating agent such as borax orEDTA or one of its sodium salts, to form stable, soluble complexes withhardness minerals, thus masking and effectively reducing the effectiveconcentration of the hardness minerals.

It has been unexpectedly discovered that ionic metallic species such asalkaline earth metal cations which normally hinder detergent activity bycomplexation as described above do not form insoluble complexes with theLAB sulfonates having a high 2-phenyl isomer content as provided hereinas readily as they do with LAB sulfonates in formulations provided by aprior art. The net result of the reluctance of such ionic metallicspecies to form insoluble complexes with LAB sulfonates having ahigh-2-phenyl isomer provided by the invention and the formulationsdescribed herein is that an effectively higher concentration of suchactive detergent components is present in solution and available forsolubilization of oils and general cleaning of exposed substrates. Thisresult is astounding, since hardness minerals have forever been an issuein the formulation of every detergent and cleaning composition becauseof their propensity to form insoluble salts with surface active agents.Thus, the formulations of this invention are pioneering insomuch as theyrepresent a first major step away from considering alkaline earthcations as being an issue in the formulation of detergents and the like.

Through use of the LAB sulfonates having a high 2-phenyl isomer contentas provided herein, formulators may in many instances omit a chelatingagent from their formulations, or at the least, only moderate, reducedamounts would be required. Since such chelants are relatively costly, asavings in manufacture from the standpoints of blending and raw materialquantities may be passed on to the public.

Cleaning compositions which utilize an alkylbenzene sulfonate of thisinvention having a 2-phenyl isomer content of about 80% in the stead ofthose having a 2-phenyl isomer content of less than about 50% are ingeneral are possessive of much greater cleaning strength. The increasein cleaning performance provided by the linear alkylbenzene sulfonatesof this invention having a 2-phenyl isomer content of about 80% (“SuperHigh 2-Phenyl”) is illustrated by the data set forth in FIG. A below. InFIG. A, the total detergency of a blend comprising a conventional linearalkylbenzene sulfonate (denoted as A225 that comprises a 2-phenyl isomercontent of about 16% to 18% of the total alkylbenzene sulfonatespresent; A225 is available from Huntsman Petrochemical Corporationlocated at 7114 North Lamar Blvd., Austin, Tex.) containing variousadded amounts of Super High 2-Phenyl is illustrated as performance fromlaundry testing data. For this series of tests, Super High 2-Phenyl wasblended with A225 holding the total amount of actives constant at 10%.The samples were tested in a 6 pot Terg-o-tometer® (US TestingCorporation) at 2 grams per liter of detergent at 100 degreesFahrenheit, using a 150 ppm hard water with a 15 minute wash cyclefollowed by a 5 minute rinse. Standardized soil swatches were used toassess the detergency. Results were obtained by measuring thereflectance of the swatches both before and after cleaning using aHunter Lab Color Quest reflectometer using the L-A-B scale. All swatcheswere run in triplicate and the results averaged. Soil swatches usedwere: dirty motor oil, dust sebum, grass stain, blood/milk/ink stain,olive oil (EMPA), clay, and clean white swatches, to measureredeposition. Both cotton and polyester/cotton blends were evaluated forall soils. The results show that the cleaning performance increases withincreasing percentage of Super High 2-Phenyl in the blend. The resultsfor the detergent which employed 100% of Super High 2-Phenyl were asmuch as 50% higher than the conventional LAS.

As mentioned above, detergents formulated using Super High 2-Phenylexhibit an increased tolerance to water hardness with respect to thoseformulated using conventional, commercially-available linear alkylbenzene sulfonate detergent components. FIG. B below provides turbiditydata to evidence the hardness tolerance of conventional LAS (linearalkyl benzene sulfonate) surfactant A225 present at about 1% aqueous atvarious levels of water hardness, as measured in NTU units (using aturbidimeter from Orbeco-Helige of Farmingdale, N.Y.), the use of whichis well known to those of ordinary skill in the art. In FIG. B, thepoint at which the solution turbidity first undergoes a dramaticincrease is the point approximately corresponding to the solubilitylimit of the complex formed by the hardness minerals found in the waterused and the detergent component. Thus, formulations which employconventional linear alkylbenzene sulfonate components similar to A225begin to experience a decrease in the effective concentration of a mainingredient at a water hardness level of around 750 ppm. Of course sucheffect will be more pronounced for consumers wishing to rationdetergents by using less soap in a given volume of water than therecommended amount, since the amount of total hardness with respect toavailable sulfonate will be greatly increased which may in some casesbind up more than half of the sulfonate present.

FIG. C provides data for the same hardness tolerance data as wasgathered for FIG. B present at about 1% aqueous; however, the LAS usedfor gathering these data was the Super High 2-Phenyl LAS. From the datain FIG. C, it is evident that significant amounts of water-insolublecompounds are not formed until a hardness level of about 1500 ppm isreached, which is about twice the hardness tolerance of conventionalmaterials. Since the formulations according to the invention containhigh amounts of the 2-phenyl isomer of linear alkylbenzene sulfonates,they not only have increased detergency power, but are also moretolerant to water hardness. Thus, less active chemical may be used in aformulation to give it equal cleaning power to prior art formulationswhich contain greater amounts of linear alkylbenzene sulfonates.Lowering the amount of active chemical in the formulation saves in rawmaterial costs, blending operations, and transportation costs, whichsavings may be passed on to the public.

FIG. D provides data for the same hardness tolerance data as wasgathered for FIGS. A and B; however the surfactant concentration wasreduced to about 0.1% aqueous to show the effect of reduced surfactantconcentration, since the point at which precipitates begin to form isdependent upon the total amount of surfactant present. In FIG. D, bothA225 and an alkylbenzene sulfonate provided according to the inventionhaving a 2-phenyl isomer are compared. From these data, it is evidentthat significant amounts of water-insoluble compounds are formed athardness levels of about 25 ppm using the conventional A225 materialwhile the Super High 2-phenyl material does not show any precipitationuntil the hardness level of four time this amount or about 100 ppm isachieved.

Since such a large number of formulations of various cleaningcompositions contain linear alkylbenzene sulfonates as a main detergentcomponent, the breadth of applicability of the discoveries according tothis invention should be readily apparent. Thus, all cleaningcompositions known in the prior art which contain sulfonated linearalkylbenzenes can be increased in effectiveness and cleaning strength bybeing reformulated to replace the sulfonated linear alkylbenzenescurrently used with a sulfonated linear alkylbenzene surfactantsprovided by this invention that have an increased percentage of 2-phenylalkylbenzene isomers. Further, since it is possible to blend an LABsulfonate having a high 2-phenyl isomer content produced in accordancewith the present invention (on the order of about 82%) with conventionalLAB sulfonates, it is also possible according to the invention toprovide an LAB sulfonate component useful for forming a detergentcomposition or cleaning formulation in which the component has a2-phenyl isomer content of any selected value between about 18% and 82%by weight based upon the total combined weight of all isomers of LABsulfonate present. As shown in Table 5, alkylbenzenes that containamounts of the 2-phenyl isomer in excess of 80% may be readily producedaccording to the instant process using the instant catalyst. As alsomentioned, formulators who make finished detergents would prefer to useLAB based surfactants having a 2-phenyl isomer content in the range fromabout 30 to 40 percent, but this level has not heretofore been availablein commercial quantities. Through use of the instant invention, a widevariety of cleaning products comprising LAB sulfonates having between30% and 40% of 2-phenyl isomer are easily achieved for the first time ona commercial scale. Below are set forth examples of some superiorformulations which employ sulfonated linear alkylbenzenes assurfactants. In each example, the LAB sulfonate is a sulfonate such asthat produced in accordance with table 2, and having a 2-phenyl isomercontent of about 81%. In the examples, the term “LAB sulfonate having81% 2-phenyl content” means an LAB sulfonate having a 2-phenyl isomercontent of 81% based upon the total of all LAB sulfonate isomers presentin the LAB sulfonate. In each of the Examples given below, all of theingredients were combined with one another and mixed until homogeneous.Then, in each case, the final mixtures were adjusted, as is doneaccording to a preferred form of the invention, to a pH in the range of10-11 using aqueous NaOH and HCl, as needed. However, any final pH levelin the range of about 7-12 is may be achieved.

It will be seen in the examples below that there are components in eachof the formulas other than the alkylbenzene surfactant component havinga high 2-phenyl isomer content. These other components are known bythose of ordinary skill in this art to be useful in formulating soaps,cleaning compositions, hard surface cleaners, laundry detergents, andthe like. For purposes of this invention and the appended claims, thewords “other components known to be useful in formulating soaps,detergents, and the like” means any material which a formulator ofordinary skill in the soap or detergent arts recognizes as adding abenefit to a combination that is intended to be used as a cleaningcomposition, regardless of the substrate that is intended to becleansed. Such includes every material that has been known in the priorart to be useful in soap and detergent formulations.

In each of the Examples which follow, all percentages are given on apercent by weight basis based on the total weight of the finishedcomposition, unless noted otherwise.

EXAMPLE 10 All Purpose Cleaner

LAB sulfonate having 81% 2-phenyl content 3.3 alkyl sulfate 1.6 coconutfatty acid 1.8 monoethanolamine 1.5 SURFONIC ® L12-6 12.4 Amine oxide0.9 Soda ash 0.7 Water 77.8 Total 100

EXAMPLE 11 Pine Oil Microemulsion

Pine Oil 20.0 SURFONIC ® L12-8 4.7 LAB sulfonate having 81% 2-phenylcontent 7.8 Isopropanol 11.0 Triethanolamine 4.7 Water 51.8 Total 100

EXAMPLE 12 Value Blend Powdered Laundry Detergent

LAB sulfonate having 81% 2-phenyl content 6.5 SURFONIC ® N-95 4.3 Sodaash 29.8 Sodium chloride 45.7 Sodium silicate 11.6 Polymer 2.1

EXAMPLE 13 Premium Blend Powdered Laundry Detergent

LAB sulfonate having 81% 2-phenyl content 7.1 Sodium alkyl sulfate 13.3Alcohol ethoxylate 2.6 Zeolites 34.7 Soda ash 19.6 Sodium silicate 1.0Sodium perborate 0.9 TAED 0.5 Sodium sulfate 19.3 Protease enzyme 0.5Cellulase enzyme 0.5 Total 100

EXAMPLE 14 Value Blend Laundry Concentrate

LAB sulfonate having 81% 2-phenyl content 18.5 SURFONIC ® N-95 75.00Monoethanolamine 6.50 Total 100

EXAMPLE 15 Value Blend Laundry Detergent

Concentrate from Example 14 7.000O Water (well) 92.168 OpticalBrightener 0.0100 Salt 0.1352 Salt 0.6148 Preservative 0.0100 Dye 0.0020Fragrance 0.0600 Total 100

EXAMPLE 16 Value Blend Laundry Concentrate

LAB sulfonate having 81% 2-phenyl content 17.4 SURFONIC ® N-95 34.8SURFONIC ® T-15 17.4 POGOL ® 300 8.0 Monoethanolamine 2.4 Water 20.0Total 100

EXAMPLE 17 Value Blend Laundry Detergent

Concentrate from Example 16 50.000 Water 44.245 Optical brightener A0.15 Sodium chloride 0.500 Polyacrylate A 2.500 Chelating agent 1.00NaOH (50.0% aq.) 0.220 Fragrance 0.300 Preservative 0.080 Melaleuca oil0.005 Total 100

EXAMPLE 18 Premium Laundry Detergent Concentrate

LAB sulfonate having 81% 2-phenyl content 18.50 SURFONIC ® N-95 75.00Monoethanolamine 6.50

EXAMPLE 19 Premium Laundry Detergent with Enzymes

Concentrate from Example 18 30.0000 Water (well) 56.2632 Opticalbrightener 0.0500 Calcium dichloride 0.1000 Sodium chloride 0.6148Preservative 0.0100 Dye 0.0020 Fragrance 0.0600 Propylene glycol 10.0000Borax 2.0000 Protease enzyme 0.7000 Lipase enzyme 0.2000 Total 100

EXAMPLE 20 Premium Liquid Dishwashing Formulation I

LAB sulfonate having 81% 2-phenyl  25.735 content De-ionized water 16.316 Magnesium hydroxide  1.133 Sodium hydroxide (38% aq.)  3.591SURFONIC ® SXS-40 (40% aq.)  15.000 Propylene glycol  6.000 Sodiumlauryl ether sulfate EO 3:1  14.286 (molecular weight = 440) (70% aq.)Cocoamidopropyl betaine (38% aq.)  15.789 Ethanol  0.0300 TetrasodiumEDTA  0.1500 Preservative  0.2000 Dye (0.8% aq.)  1.0000 Fragrance 0.5000 Total 100

EXAMPLE 21 Premium Liquid Dishwashing Formulation II

LAB sulfonate having 81% 2-phenyl  10.200 content De-ionized water 35.567 Magnesium hydroxide  1.133 Sodium hydroxide (38% aq.)  1.250SURFONIC ® SXS-40 (40% aq.)  15.000 Propylene glycol  6.000 Sodiumlauryl ether sulfate (40% aq.)  20.000 (molecular weight = 440) Alkylpolyglycoside (50% aq.)  6.000 Fatty acid MEA amide  3.000 TetrasodiumEDTA  0.150 Preservative  0.200 Fragrance  0.500 Total 100

The above examples are intended to be exemplary of the versatility ofthe compositions produced according to the invention with respect to theformulation of household and commercial cleaning formulations, and arenot intended to be delimitive thereof in any way whatsoever. Anyformulation of a soap, detergent, cleaning composition, whether liquidor solid, regardless of its intended use, that currently contains a LABsulfonate as a component can be increased in effectiveness by having thecurrent commercial LAB sulfonate component used in its formulationremoved and a LAB sulfonate component having an elevated 2-phenyl isomercontent substituted therefor. The present invention thus represents arevolutionary advance in the detergent arts, since the preferred2-phenyl isomer may now be produced in high yield for approximately thesame cost as inferior prior art LAB sulfonate mixtures.

It has also been discovered that salts of alkylbenzene sulfonates havinga 2-phenyl isomer content greater than about 60% may be isolated assolids at room temperature. This result is surprising since salts ofalkylbenzene sulfonates have heretofore been believed to exist only inliquid form. Thus, by the present invention, it is now possible toprovide dry powder formulations comprising alkylbenzene sulfonates, suchas dry laundry detergents, dry dishwashing detergents, etc. Such dryformulations may be provided using existing blending techniques,including the use of conventional dry processing equipment such asribbon blenders, etc., and also include detergent tablets for laundryuse.

To produce a solid alkylbenzene salt according to a preferred form ofthe invention, one begins with the sulfonic acid mixture which isproduced from sulfonating an alkylbenzene mixture prepared in accordancewith the invention, such as any of samples 4 through 7 of table 2 above,which contain more than about 80.0% of the 2-phenyl isomers. Suchsulfonic acids are then dissolved in water to a concentration of about10.0% by weight, and neutralized by slow addition of an alkaline aqueoussolution of the desired cation, such as through the use of alkalihydroxides, until stoichiometric neutralization has occurred, which inthe case of sodium and potassium is when a pH of about 10.5 is reached.Finally, the water is removed by evaporation or by other means known tothose skilled in the chemical arts, such as through the use of aROTOVAP® evaporator or the like, thus leaving crystals of thealkylbenzene sulfonate salt. Such crystals may be conveniently purifiedfurther by recrystallization from ethanol. The sodium salts ofalkylbenzene sulfonate according to sample 4 of table 2 have a meltingpoint of about 84 degrees centigrade, and the potassium salts ofalkylbenzene sulfonate have a melting point of about 65 degreescentigrade using differential scanning calorimetry according to ASTMspecification D-3417.

Cationic surfactants may also function as a cation in forming a stable,solid salt of an alkylbenzene sulfonate. Cationic surfactants are wellknown in the art as being surfactants with a positively-charged ionicgroup in their molecular structure, such as the as quaternary ammoniumcompounds. Cationic surfactants are known to function together withother parts of a formulated detergent system to lower the water'ssurface tension. They are typically used in wash, rinse and dryer-addedfabric softeners. Thus, when a cationic surfactant is employed forproviding charge balance in a solid alkylbenzene sulfonate saltaccording to the invention, a formulator using such a salt is able toreap added benefit from the presence of both a cationic surfactant andan anionic surfactant in the same solid material, which may be powdered.Such salts therefore may reduce the costs associated with storage andblending of different materials, as is currently common in the art owingto the presence of both a surfactant and a detergent in the samemolecule.

Owing to the unexpected finding that certain salts of the alkylbenzenesulfonates having sufficient 2-phenyl isomer content are solids at roomtemperature, the present invention also comprises as formulations usefulfor cleaning laundry which comprise solid tablets, as well as solid barsof soap comprising the solid alkylbenzene sulfonates as an activedetergent component.

Detergent tablets are described, for example, in GB 911 204 (Unilever),U.S. Pat. No. 3,953,350 (Kao), JP 60 015 500A (Lion), JP 60 135 497A(Lion) and JP 60 135 498A (Lion); and are sold commercially in Spain.Detergent tablets are generally made by compressing or compacting adetergent powder, as is well-known in the art. Thus, the presentinvention contemplates substitution of at least a portion of, and morepreferably all of, the active detergent component of a conventionallaundry tablet of the prior art with a salt of an alkylbenzene sulfonatehaving sufficiently high 2-phenyl isomer to cause such salt to exist inthe form of a solid at room temperature. Such substitution is readilymade by providing such solid sulfonate in the stead of the conventionaldetergent component of the conventional laundry tablet during laundrytablet manufacture.

Bars of soap are made by various means known to those in the artincluding the pouring into molds of a caustic/oil mixture prior to itsfull saponification, or the use of “soap noodles” in a press with orwithout the aid of heat and pressure. Soaps typically include fatty acidcarboxylates, perfumes, dyes, preservatives, bactericides, fillers suchas talc, and other additives. The present invention contemplatessubstitution of at least a portion of, and more preferably all of, theactive cleaning component of a conventional bar of soap of the prior artwith a salt of an alkylbenzene sulfonate having sufficiently high2-phenyl isomer to cause such salt to exist in the form of a solid atroom temperature. Such substitution is readily made by providing suchsolid sulfonate in the stead of the conventional detergent component ofthe conventional bar of soap during soap manufacture. Thus, a bar ofsoap according to the invention may comprise only the Super High2-phenyl alkylbenzene sulfonate according to the invention, incombination with sufficient binders, perfumes, dyes, etc. to form asolid bar of soap, using in one form of the invention the same generalcompression techniques useful for producing laundry tablets.

Although the present invention has been shown and described with respectto certain preferred embodiments, it is obvious that equivalentalterations and modifications will occur to others skilled in the artupon the reading and understanding of the specification. The presentinvention includes all such equivalent alterations and modifications,and is limited only by the scope of the claims which now follow.

What is claimed is:
 1. A composition useful as a detergent for cleaninglaundry, dishes, and hard surfaces, that is formed from componentscomprising: a) an alkylbenzene sulfonate surfactant component present inany amount between 0.25% and 99.50% by weight based upon the totalweight of the composition, said component characterized as consistingessentially of any amount between 42.00% and 82.00% by weight based uponthe total weight of the component, including every hundredth percentagetherebetween, of water-soluble sulfonates of the 2-phenyl isomers ofalkylbenzenes described by the general formula:

 wherein n is equal to any integer between 4 and 16; and b) any amountbetween 99.75% and 0.50% of a second component that comprises at leastone other component known to be useful in formulating soaps, detergents,and the like, wherein at least one of said other components is selectedfrom the group consisting of: fatty acids, alkyl sulfates, anethanolamine, an amine oxide, alkali carbonates, water, ethanol,isopropanol, pine oil, sodium chloride, sodium silicate, polymers,alcohol alkoxylates, zeolites, perborate salts, alkali sulfates,enzymes, hydrotropes, dyes, fragrances, preservatives, brighteners,builders, polyacrylates, essential oils, alkali hydroxides,water-soluble branched alkylbenzene sulfonates, ether sulfates,alkylphenol alkoxylates, fatty acid amides, alpha olefin sulfonates,paraffin sulfonates, betaines, chelating agents, tallowamineethoxylates, polyetheramine ethoxylates, ethylene oxide/propylene oxideblock copolymers, alcohol ethylene oxide/propylene oxide low foamsurfactants, methyl ester sulfonates, alkyl polysaccharides, N-methylglucamides, alkylated sulfonated diphenyl oxide, polyethylene glycol,and water soluble alkylbenzene sulfonates having a 2-phenyl isomercontent of less than 30.00%, subject to the proviso that when saidsecond component is selected to be water soluble alkylbenzene sulfonateshaving a 2-phenyl isomer content of less than 30.00%, the total amountof 2-phenyl isomers of all alkylbenzene sulfonate surfactants present isless than 40.00% on a weight basis.
 2. A composition according to claim1 wherein the 2-phenyl isomers content of the alkylbenzene sulfonatesurfactant component comprises any amount between 45.00% and 82.00% byweight based upon the total weight of the component, including everyhundredth percentage therebetween.
 3. A composition according to claim 1wherein the 2-phenyl isomers content of the alkylbenzene sulfonatesurfactant component comprises any amount between 57.00% and 82.00% byweight based upon the total weight of the component, including everyhundredth percentage therebetween.
 4. A composition according to claim 1wherein said alkylbenzene sulfonate surfactant component is present inany amount between 1.00% and 25.00% by weight based upon the totalweight of said composition useful as a detergent.
 5. A composition as inclaim 1 wherein the alkylbenzene sulfonate surfactant componentcomprises one alkyl group bonded to a benzene ring, and wherein saidalkyl group comprises any integral number of carbon atoms between 7 and16.
 6. A composition as in claim 1 wherein the alkylbenzene sulfonatesurfactant component comprises one alkyl group bonded to a benzene ring,and wherein said alkyl group is substantially linear.
 7. A compositionas in claim 1 wherein the alkylbenzene sulfonate surfactant componentcomprises one alkyl group bonded to a benzene ring, and wherein saidalkyl group is a branched alkyl.
 8. A composition according to claim 1wherein said second component is present in any amount between 0.10% and25.00% by weight based upon the total weight of said composition usefulas a detergent.
 9. A composition according to claim 1 wherein saidsecond component is a mixture of branched alkylbenzene sulfonateswherein said branched alkylbenzene sulfonates comprise one branchedalkyl group bonded to a benzene ring, and wherein said alkyl groupcomprises any integral number of carbon atoms between 7 and
 16. 10. Acomposition according to claim 1 further comprising a third component,wherein said third component is different from said second component andis selected from the group consisting of: at least one other componentknown to be useful in formulating soaps, detergents, and the like,wherein at least one of said other components is selected from the groupconsisting of: fatty acids, alkyl sulfates, an ethanolamine, an amineoxide, alkali carbonates, water, ethanol, isopropanol, pine oil, sodiumchloride, sodium silicate, polymers, alcohol alkoxylates, zeolites,perborate salts, alkali sulfates, enzymes, hydrotropes, dyes,fragrances, preservatives, brighteners, builders, polyacrylates,essential oils, alkali hydroxides, water-soluble branched alkylbenzenesulfonates, and water soluble alkylbenzene sulfonates having a 2-phenylisomer content of less than 30.00%.
 11. A composition according to claim10 wherein said third component is a mixture of water solublealkylbenzene sulfonates wherein said water soluble alkylbenzenesulfonates have a 2-phenyl isomer content of less than 25.00% by weightbased upon the total weight of said water soluble alkylbenzene sulfonatecomponent.
 12. A composition as in claim 1 wherein the alkylbenzenesulfonate surfactant component contains an effective amount of 2-phenylisomer to provide a turbidity in a cleaning solution formed from mixingsaid composition and water of below 200 NTU units when the totalhardness level of the water is any value between 100-300 ppm, and thealkylbenzene sulfonate surfactant concentration in the cleaning solutionis any amount between 0.09 and 0.11%.
 13. A composition as in claim 1wherein the alkylbenzene sulfonate surfactant component contains aneffective amount of 2-phenyl isomer to provide a turbidity in a cleaningsolution formed from mixing said composition and water of below 150 NTUunits when the total hardness level of the water is about 200 ppm, andin which the surfactant concentration in the cleaning solution is anyamount between 0.09 and 0.11%.
 14. A composition as in claim 1 whereinthe alkylbenzene sulfonate surfactant component contains an effectiveamount of 2-phenyl isomer to provide a turbidity in a cleaning solutionformed from mixing said composition and water of below 50 NTU units whenthe total hardness level of the water is 1400 ppm and in which thesurfactant concentration in the cleaning solution is any amount between0.90 and 1.10%.
 15. A salt of an alkylbenzene sulfonate, which saltcomprises an effective amount of the 2-phenyl isomer of alkylbenzenesdescribed by the general formula:

for rendering said salt to exist in the form of a solid at roomtemperature, wherein n is equal to any integer between 4 and 16 whereinthe 2-phenyl isomer content of such alkyl benzene sulfonate salts is42%-82% by weight based on the total weight of the alkyl benzenesulfonate.
 16. A mixture of salts of alkylbenzene sulfonates whereinsaid alkylbenzene sulfonates comprise a single alkyl substituentselected from any carbon number in the detergent range bonded to abenzene ring to which benzene ring a sulfonate group is also bonded,wherein the 2-phenyl isomer content of such alkylbenzene sulfonate saltsis 42%-82% by weight based on the total weight of the alkyl benzenesulfonate.
 17. A mixture of salts according to claim 16 having a meltingpoint peak in the range of between 60 degrees centigrade and 90 degreescentigrade as measured by differential scanning calorimetry according toASTM method D-3417.
 18. A mixture of salts of an alkylbenzene sulfonateas in claim 16 wherein said salt comprises a cation selected from thegroup consisting of: alkali metal cations, alkaline earth metal cations,ammonium ions, and cationic surfactants.
 19. A mixture of salts of analkylbenzene sulfonate as in claim 18 wherein said cation is selectedfrom the group consisting of: sodium and potassium.
 20. A solid bar ofsoap comprising between 3.00% and 25.00% by weight of a salt of 2-phenylisomers of alkylbenzene sulfonate, including every hundredth percentagetherebetween, which salt comprises an effective amount of the 2-phenylisomers of alkylbenzenes described by the general formula:

for rendering said salt to exist in the form of a solid at roomtemperature, wherein n is equal to any integer between 4 and 16 whereinthe 2-phenyl isomer content of such alkyl benzene sulfonate salts is42%-82% by weight based on the total weight of the alkyl benzenesulfonate.
 21. A free-flowing powdered detergent formulation whichcontains a solid salt of an alkylbenzene sulfonate and at least oneother component known to be useful in formulating soaps, detergents, andthe like, wherein said salt comprise, an effective amount of the2-phenyl isomers of alkylbenzenes described by the general formula:

for rendering said salt to exist in the form of a solid at roomtemperature, wherein n is equal to any integer between 4 and 16 whereinthe 2-phenyl isomer content of such alkyl benzene sulfonate salts is42%-82% by weight based on the total weight of the alkyl benzenesulfonate.
 22. A solid tablet useful for cleaning laundry whichcomprises a solid salt of an alkylbenzene sulfonate and at least oneother component known to be useful in formulating soaps, detergents, andthe like, wherein said salt comprises an effective amount of the2-phenyl isomers of alkylbenzenes described by the general formula:

for rendering said salt to exist in the form of a solid at roomtemperature, wherein n is equal to any integer between 4 and 16 whereinthe 2-phenyl isomer content of such alkyl benzene sulfonate salts is42%-82% by weight based on the total weight of the alkyl benzenesulfonate.